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USGS2013

Iron mineralogy and bioaccessibility of dust generated from soils as determined by reflectance spectroscopy and magnetic and chemical properties--Nellis Dunes recreational area, Nevada

Atmospheric mineral dust exerts many important effects on the Earth system, such as atmospheric temperatures, marine productivity, and melting of snow and ice. Mineral dust also can have detrimental effects on human health through respiration of very small particles and the leaching of metals in various organs. These effects can be better understood through characterization of the physical and chemical properties of dust, including certain iron oxide minerals, for their extraordinary radiative properties and possible effects on lung inflammation. Studies of dust from the Nellis Dunes recreation area near Las Vegas, Nevada, focus on characteristics of radiative properties (capacity of dust to absorb solar radiation), iron oxide mineral type and size, chemistry, and bioaccessibility of metals in fluids that simulate human gastric, lung, and phagolysosomal fluids. In samples of dust from the Nellis Dunes recreation area with median grain sizes of 2.4, 3.1, and 4.3 micrometers, the ferric oxide minerals goethite and hematite, at least some of it nanosized, were identified. In one sample, in vitro bioaccessibility experiments revealed high bioaccessibility of arsenic in all three biofluids and higher leachate concentration and bioaccessibility for copper, uranium, and vanadium in the simulated lung fluid than in the phagolysosomal fluid. The combination of methods used here to characterize mineral dust at the Nellis Dunes recreation area can be applied to global dust and broad issues of public health.

Nevada↗

USGS2013

Hydration free energies of cyanide and hydroxide ions from molecular dynamics simulations with accurate force fields

The evaluation of hydration free energies is a sensitive test to assess force fields used in atomistic simulations. We showed recently that the vibrational relaxation times, 1D- and 2D-infrared spectroscopies for CN(-) in water can be quantitatively described from molecular dynamics (MD) simulations with multipolar force fields and slightly enlarged van der Waals radii for the C- and N-atoms. To validate such an approach, the present work investigates the solvation free energy of cyanide in water using MD simulations with accurate multipolar electrostatics. It is found that larger van der Waals radii are indeed necessary to obtain results close to the experimental values when a multipolar force field is used. For CN(-), the van der Waals ranges refined in our previous work yield hydration free energy between -72.0 and -77.2 kcal mol(-1), which is in excellent agreement with the experimental data. In addition to the cyanide ion, we also study the hydroxide ion to show that the method used here is readily applicable to similar systems. Hydration free energies are found to sensitively depend on the intermolecular interactions, while bonded interactions are less important, as expected. We also investigate in the present work the possibility of applying the multipolar force field in scoring trajectories generated using computationally inexpensive methods, which should be useful in broader parametrization studies with reduced computational resources, as scoring is much faster than the generation of the trajectories.

Physical Chemistry Chemical Physics↗

USGS2015

Detailed description of oil shale organic and mineralogical heterogeneity via fourier transform infrared mircoscopy

Mineralogical and geochemical information on reservoir and source rocks is necessary to assess and produce from petroleum systems. The standard methods in the petroleum industry for obtaining these properties are bulk measurements on homogenized, generally crushed, and pulverized rock samples and can take from hours to days to perform. New methods using Fourier transform infrared (FTIR) spectroscopy have been developed to more rapidly obtain information on mineralogy and geochemistry. However, these methods are also typically performed on bulk, homogenized samples. We present a new approach to rock sample characterization incorporating multivariate analysis and FTIR microscopy to provide non-destructive, spatially resolved mineralogy and geochemistry on whole rock samples. We are able to predict bulk mineralogy and organic carbon content within the same margin of error as standard characterization techniques, including X-ray diffraction (XRD) and total organic carbon (TOC) analysis. Validation of the method was performed using two oil shale samples from the Green River Formation in the Piceance Basin with differing sedimentary structures. One sample represents laminated Green River oil shales, and the other is representative of oil shale breccia. The FTIR microscopy results on the oil shales agree with XRD and LECO TOC data from the homogenized samples but also give additional detail regarding sample heterogeneity by providing information on the distribution of mineral phases and organic content. While measurements for this study were performed on oil shales, the method could also be applied to other geological samples, such as other mudrocks, complex carbonates, and soils.

Energy & Fuels↗

USGS2022

Hydrogen isotope behavior during rhyolite glass hydration under hydrothermal conditions

The diffusion of molecular water (H 2 O m ) from the environment into volcanic glass can hydrate the glass up to several wt% at low temperature over long timescales. During this process, the water imprints its hydrogen isotope composition (δD H2O ) to the glass (δD gl ) offset by a glass-H 2 O fractionation factor (ΔD gl-H2O = δD gl – δD H2O ) which is approximately −33‰ at Earth surface temperatures. Glasses hydrate much more rapidly at higher, sub-magmatic temperatures as they interact with H 2 O during eruption, transport, and emplacement. To aid in the interpretation of δD gl in natural samples, we present hydrogen isotope results from vapor hydration experiments conducted at 175–375 °C for durations of hours to months using natural volcanic glasses. The results can be divided into two thermal regimes: above 250 °C and below 250 °C. Lower temperature experiments yield raw ΔD gl-H2O values in the range of −33 ± 11‰. Experiments at 225 °C using both positive and negative initial ΔD gl-H2O values converge on this range of values, suggesting this range represents the approximate equilibrium fractionation for H isotopes between glass and H 2 O vapor (10 3 lnα gl-H2O ) below 250 °C. Variation in ΔD gl-H2O (−33 ± 11‰) between different experiments and glasses may arise from incomplete hydration, analytical uncertainty, differences in glass chemistry, and/or subordinate kinetic isotope effects. Experiments above 250 °C yield unexpectedly low δD gl values with ΔD gl-H2O values of ≤–85‰. While alteration alone is incapable of explaining the data, these run products have more extensive surface alteration and are not interpreted to reflect equilibrium fractionation between glass and H 2 O vapor. Fourier transform infrared spectroscopy (FTIR) shows that glass can hydrate with as much as 5.9 wt% H 2 O m and 1.0 wt% hydroxl (OH − ) in the highest P-T experiment at 375 °C and 21.1 MPa. Therefore, we employ a 1D isotope diffusion–reaction model of glass hydration to evaluate the roles of equilibrium fractionation, isotope diffusion, water speciation reactions internal to the glass, and changing boundary conditions (e.g. alteration and dissolution). At lower temperatures, the best fitting model results to experimental data for low silica rhyolite (LSR) glasses require only an equilibrium fractionation factor and yield 10 3 lnα gl-H2O values of −33‰ ± 5‰ and −25‰ ± 5‰ at 175 °C and 225 °C, respectively. At higher temperatures, ΔD gl-H2O is dominated by boundary layer effects during glass hydration and glass surface alteration. The modeled bulk δD gl value is highly responsive to changes in the δD gl boundary condition regardless of the magnitude of other kinetic effects. Observed glass dissolution and surficial secondary mineral formation are likely to impose a disequilibrium boundary layer that drives extreme δD gl fractionation with progressive glass hydration. These results indicate that the observed ΔD gl-H2O of ∼−33 ± 11‰ can be cautiously applied as an equilibrium 10 3 lnα gl-H2O value to natural silicic glasses hydrated below 250 °C to identify hydration sources. This approximate ΔD gl-H2O may be applicable to even higher temperature glasses hydrated on short timescales (of seconds to minutes) in phreatomagmatic or submarine eruptions before H 2 O in the glass is primarily affected by boundary layer effects associated with alteration on the glass surface.

Geochimica et Cosmochimica Acta↗

USGS2024

Hyperspectral mapping of magmatic-hydrothermal sericite, Battle Mountain mining district, Nevada

We demonstrate the utility of multi-scale imaging spectroscopy data (hyperspectral data) to differentiate magmatic-hydrothermal sericite from other white micas based on grain size, in a case study of the Battle Mountain mining district in Humboldt and Lander Counties, Nevada. The Battle Mountain mining district contains porphyry, skarn, and distal disseminated deposits that formed in magmatic-hydrothermal systems, as well as sedimentary-rock hosted gold deposits of less certain origin. We generated spectral-based mineral maps of the Battle Mountain mining district to examine the spatial distribution of spectrally dominant minerals such as kaolinite, montmorillonite , and white micas (muscovite, sericite, and illite). We then used spectral-based mineral mapping to characterize the grain size and composition of white micas, enabling us to differentiate igneous muscovite from magmatic-hydrothermal sericite. By integrating our spectral-based maps with geologic mapping, airborne aeromagnetic data, and prior studies on mines and deposits in Battle Mountain, we determined that finer grained, higher Al sericite spatially correlated with the footprints of known magmatic-hydrothermal systems and is interpreted as forming from magmatic-hydrothermal alteration. Larger grained, lower Al muscovites are distal from known magmatic-hydrothermal systems and are interpreted as being igneous derived siliciclastic sediments that became constituents of the host sedimentary rocks. Techniques described in this contribution can be applied to any appropriate hyperspectral data, regardless of sensor type used to collect the data.

Nevada↗

USGS2021

Organo-facies and mineral effects on sorption capacity of low-maturity Permian Barakar shales from the Auranga Basin, Jharkhand, India

Shales associated with the Lower Permian (Barakar Formation) sediments of the Auranga Coalfield, India, occur in the immature–early mature stage. The sorption capacity of Barakar shale samples has been studied through high-pressure methane (CH 4 ) adsorption and low-pressure N 2 gas adsorption (LPN 2 GA) methods, supported with proximate analyses, programmed pyrolysis, optical petrography, and with energy-dispersive spectroscopy, X-ray diffraction, and inductively coupled plasma mass spectrometry. The sorption capacity is a function of the organic and inorganic constituents present in the shale samples. The methane sorption capacity (MSC) and Langmuir volume of the shale samples vary from 0.217 to 0.314 and 0.315 to 0.429 mmol/g rock, respectively. The BET-calculated surface area of the studied shales varies from 8.12 to 30.36 m 2 /g. The sorption capacities show the importance of the total organic content (TOC) through weak but positive correlations with MSC ( r 2 = 0.45) and S 1 values (mg hydrocarbons/g rock from programmed pyrolysis; r 2 = 0.40). Moreover, apparent inverse relationships were observed between MSC and clay mineral abundances, suggesting that individual clay mineral types may influence MSC, although more work is needed. The TOC-normalized MSC (MSC*) of shale samples shows a positive trend with quartz plus clay mineral content and ash yield of r 2 = 0.64 for both. In addition, MSC* shows a negative logarithmic relationship with S 1 + S 2 ( r 2 = 0.63) and a positive linear relationship with TOC-normalized total organic matter (TOM*) ( r 2 = 0.88, when 5 low TOM* samples are excluded) indicating complex relationships possibly including bitumen retention in the sample pore spaces. The micropore study of the samples through LPN 2 GA, applying Dubinin–Radushkevich, Dubinin–Astakhov, and density functional theory models, shows the dominance of micro-mesopore concentrations in the shale matrix of ∼2 nm pore diameter. However, these pores might be present as blind or closed pores. The presence of thorium and zirconium is reflective of terrigenous detrital matter, i.e., moderately to strongly recycled sediments. The fluviatile facies of deposited shales in the Auranga Coalfield are noted by the significant presence of kaolinite (32.5–78.3%), which suggests the importance of its effect on the sorption capacity of proximal terrigenous shales.

Jharkhand↗

USGS2024

In situ lung dust analysis by automated Field Emission Scanning Electron Microscopy with Energy Dispersive X-ray Spectroscopy: A method for assessing inorganic particles in tissue from coal miners

Context.— Overexposure to respirable coal mine dust can cause severe lung disease including progressive massive fibrosis (PMF). Field emission scanning electron microscopy with energy dispersive x-ray spectroscopy (FESEM-EDS) has been used for in situ lung dust particle analysis for evaluation of disease etiology. Automating such work can reduce time, costs, and user bias. Objective.— To develop and test an automated FESEM-EDS method for in situ analysis of inorganic particles in coal miner lung tissue. Design.— We programmed an automated FESEM-EDS procedure to collect particle size and elemental data, using lung tissue from 10 underground coal miners with PMF and 4 control cases. A statistical clustering approach was used to establish classification criteria based on particle chemistry. Data were correlated to PMF/non-PMF areas of the tissue, using corresponding brightfield microscopy images. Results for each miner case were compared with a separate corresponding analysis of particles recovered following tissue digestion. Results.— In situ analysis of miner tissues showed higher particle number densities than controls and densities were generally higher in PMF than non-PMF areas. Particle counts were typically dominated by aluminum silicates with varying percentages of silica. Compared to digestion results for the miner tissues, in situ results indicated lower density of particles (number per tissue volume), larger size, and a lower ratio of silica to total silicates—probably due to frequent particle clustering in situ. Conclusions.— Automated FESEM-EDS analysis of lung dust is feasible in situ and could be applied to a larger set of mineral dust–exposed lung tissues to investigate specific histologic features of PMF and other dust-related occupational diseases.

Archives of Pathology↗

USGS2005

Freshwater mussel shells as environmental chronicles: Geochemical and taphonomic signatures of mercury-related extirpations in the North Fork Holston River, Virginia

This study utilized freshwater mussel shells to assess mercury (Hg) contamination in the North Fork Holston River that extirpated (caused local extinctions of) a diverse mussel fauna. Shells (n = 366) were collected from five sites situated upstream (two sites), just below (one site), and downstream (two sites) of the town of Saltville, Virginia, where Hg was used to produce chlorine and caustic soda from 1950 to 1972. Shell samples were used to test the (1) utility of geochemical signatures of shells for assessing the spatial variation in Hg levels in the river relative to the contamination source and (2) value of taphonomy (postmortem shell alteration) for distinguishing sites that differ in extirpation histories. Geochemical signatures of 40 shells, analyzed using atomic absorption spectroscopy, indicated a strong longitudinal pattern. All shells from the two upstream sites had low Hg concentrations (<5-31 ??g/kg), shells directly below Saltville had variable, but dramatically higher concentrations (23-4637 ??g/kg), and shells from the two downstream sites displayed intermediate Hg levels (<5-115 ??g/kg) that declined with distance from Saltville. Two pre-industrial shells, collected at Saltville in 1917, yielded very low Hg estimates (5-6 ??g/kg). Hg signatures were consistent among mussel species, suggesting that Hg concentrations were invariant to species type; most likely, highly variable Hg levels, both across sites and through time, overwhelmed any interspecific differences in Hg acquisition. Also, a notable postmortem incorporation of Hg in mussel shells seemed unlikely, as the Hg content was not correlated with shell taphonomy (r = 0.18; p = 0.28). The taphonomic analysis (n = 366) showed that the degree of shell alteration reliably distinguished sites with different extirpation histories. At Saltville, where live mussels have been absent for at least 30 years, shells were most heavily altered and fragmented. Conversely, fresh-looking shells abounded upstream, where reproducing mussel populations are still present. In summary, relic shells offered valuable spatiotemporal data on Hg concentrations in a polluted ecosystem, and shell taphonomic signatures discriminated sites with different extirpation histories. The shell-based strategies exemplified here do not require sampling live specimens and may augment more standard strategies applied to environmental monitoring. The approach should prove especially useful in areas with unknown extirpation and pollution histories. ?? 2005 American Chemical Society.

Environmental Science & Technology↗

USGS2018

Accurate predictions of microscale oxygen barometry in basaltic glasses using V K-edge X-ray absorption spectroscopy: A multivariate approach

Because magmatic oxygen fugacity ( f O2 ) exerts a primary control on the discrete vanadium (V) valence states that will exist in quenched melts, V valence proxies for f O2 , measured using X-ray absorption near-edge spectroscopy (XANES), can provide highly sensitive measurements of the redox conditions in basaltic melts. However, published calibrations for basaltic glasses primarily relate measured intensities of specific spectral features to V valence or oxygen fugacity. These models have not exploited information contained within the entire XANES spectrum, which also provide a measure of changes in V chemical state as a function of f O2 . Multivariate analysis (MVA) holds significant promise for the development of calibration models that employ the full XANES spectral range. In this study, new calibration models are developed using MVA partial least-squares (PLS) regression and least absolute shrinkage and selection operator (Lasso) regression to predict the f O2 of equilibration in glasses of basaltic composition directly. The models are then tested on a suite of natural glasses from mid-ocean ridge basalts and from Kilauea. The models relate the measured XANES spectral features directly to buffer-relative f O2 as the predicted variable, avoiding the need for an external measure of the V valence in the experimental glasses used to train the models. It is also shown that by predicting buffer-relative f O2 directly, these models also minimize temperature-relative uncertainties in the calibration. The calibration developed using the Lasso regression model, using a Lasso hyperparameter value of α = 0.0008, yields nickel-nickel oxide (NNO) relative f O2 predictions with a root-mean-square-error of ±0.33 log units. When applied to natural basaltic glasses, the V MVA calibration model generally yields predicted NNO-relative f O2 values that are within the analytical uncertainty of what is calculated using Fe XANES to predict Fe 3+ /ΣFe. When applied to samples of natural basaltic glass collected in 2014 from an active lava flow at Kilauea, a mean f O2 of NNO-1.15 ± 0.19 (1σ) is calculated, which is generally consistent with other published f O2 estimates for subaerial Kilauea lavas. When applied to a sample of pillow-rim basaltic glass dredged from the East Pacific Rise, calculated f O2 varies from NNO-2.67 (±0.33) to NNO-3.72 (±0.33) with distance from the quenched pillow rim. Fe oxybarometry in this sample provides an f O2 of NNO-2.54 ± 0.19 (1σ), which is in good agreement with that provided by the V oxybarometry within the uncertainties of the modeling. However, the data may indicate that V XANES oxybarometry has greater sensitivity to small changes in f O2 at these more reduced redox conditions than can be detected using Fe XANES.

Hawaii↗

USGS1997

Arsenic and lead concentrations in the Pond Creek and Fire Clay coal beds, eastern Kentucky coal field

The Middle Pennsylvanian Breathitt Formation (Westphalian B) Pond Creek and Fire Clay coal beds are the 2 largest producing coal beds in eastern Kentucky. Single channel samples from 22 localities in the Pond Creek coal bed were obtained from active coal mines in Pike and Martin Countries, Kentucky, and a total of 18 Fire Clay coal bed channel samples were collected from localities in the central portion of the coal field. The overall objective of this study was to investigate the concentration and distribution of potentially hazardous elements in the Fire Clay and Pond Creek coal beds, with particular emphasis on As and Pb, 2 elements that are included in the 1990 Clean Air Act Amendments as potential air toxics. The 2 coals are discussed individually as the depositional histories are distinct, the Fire Clay coal bed having more sites where relatively high-S lithologies are encountered. In an effort to characterize these coals, 40 whole channel samples, excluding 1-cm partings, were analyzed for major, minor and trace elements by X-ray fluorescence and proton-induced X-ray emission spectroscopy. Previously analyzed samples were added to provide additional geographic coverage and lithotype samples from one site were analyzed in order to provide detail of vertical elemental trends. The As and Pb levels in the Fire Clay coal bed tend to be higher than in the Pond Creek coal bed. One whole channel sample of the Fire Clay coal bed contains 1156 ppm As (ash basis), with a single lithotype containing 4000 ppm As (ash basis). Most of the As and Pb appears to be associated with pyrite, which potentially can be removed in beneficiation (particularly coarser pyrite). Disseminated finer pyrite may not be completely removable by cleaning. In the examination of pyrite conducted in this study, it does not appear that significant concentration of As or Pb occurs in the finer pyrite forms. The biggest potential problem of As- or Pb-enriched pyrite is, therefore, one of refuse disposal.

Applied Geochemistry↗

USGS1999

Estimation of methanogen biomass via quantitation of coenzyme M

Determination of the role of methanogenic bacteria in an anaerobic ecosystem often requires quantitation of the organisms. Because of the extreme oxygen sensitivity of these organisms and the inherent limitations of cultural techniques, an accurate biomass value is very difficult to obtain. We standardized a simple method for estimating methanogen biomass in a variety of environmental matrices. In this procedure we used the thiol biomarker coenzyme M (CoM) (2-mercaptoethanesulfonic acid), which is known to be present in all methanogenic bacteria. A high-performance liquid chromatography-based method for detecting thiols in pore water (A. Vairavamurthy and M. Mopper, Anal. Chim. Acta 78:363–370, 1990) was modified in order to quantify CoM in pure cultures, sediments, and sewage water samples. The identity of the CoM derivative was verified by using liquid chromatography-mass spectroscopy. The assay was linear for CoM amounts ranging from 2 to 2,000 pmol, and the detection limit was 2 pmol of CoM/ml of sample. CoM was not adsorbed to sediments. The methanogens tested contained an average of 19.5 nmol of CoM/mg of protein and 0.39 ± 0.07 fmol of CoM/cell. Environmental samples contained an average of 0.41 ± 0.17 fmol/cell based on most-probable-number estimates. CoM was extracted by using 1% tri-( N )-butylphosphine in isopropanol. More than 90% of the CoM was recovered from pure cultures and environmental samples. We observed no interference from sediments in the CoM recovery process, and the method could be completed aerobically within 3 h. Freezing sediment samples resulted in 46 to 83% decreases in the amounts of detectable CoM, whereas freezing had no effect on the amounts of CoM determined in pure cultures. The method described here provides a quick and relatively simple way to estimate methanogenic biomass.

Applied and Environmental Microbiology↗

USGS2004

Surface complexation model of uranyl sorption on Georgia kaolinite

The adsorption of uranyl on standard Georgia kaolinites (KGa-1 and KGa-1B) was studied as a function of pH (3–10), total U (1 and 10 μmol/l), and mass loading of clay (4 and 40 g/l). The uptake of uranyl in air-equilibrated systems increased with pH and reached a maximum in the near-neutral pH range. At higher pH values, the sorption decreased due to the presence of aqueous uranyl carbonate complexes. One kaolinite sample was examined after the uranyl uptake experiments by transmission electron microscopy (TEM), using energy dispersive X-ray spectroscopy (EDS) to determine the U content. It was found that uraniumwas preferentially adsorbed by Ti-rich impurity phases (predominantly anatase), which are present in the kaolinite samples. Uranyl sorption on the Georgia kaolinites was simulated with U sorption reactions on both titanol and aluminol sites, using a simple non-electrostatic surface complexation model (SCM). The relative amounts of U-binding >TiOH and >AlOH sites were estimated from the TEM/EDS results. A ternary uranyl carbonate complex on the titanol site improved the fit to the experimental data in the higher pH range. The final model contained only three optimised log K values, and was able to simulate adsorption data across a wide range of experimental conditions. The >TiOH (anatase) sites appear to play an important role in retaining U at low uranyl concentrations. As kaolinite often contains trace TiO 2 , its presence may need to be taken into account when modelling the results of sorption experiments with radionuclides or trace metals on kaolinite.

Applied Clay Science↗

USGS1986

Organic geochemical analysis of sedimentary organic matter associated with uranium

Samples of sedimentary organic matter from several geologic environments and ages which are enriched in uranium (56 ppm to 12%) have been characterized. The three analytical techniqyes used to study the samples were Rock-Eval pyrolysis, pyrolysis-gas chromatography-mass spectrometry, and solid-state C-13 nuclear magnetic resonance (NMR) spectroscopy. In samples with low uranium content, the pyrolysis-gas chromatography products contain oxygenated functional groups (as hydroxyl) and molecules with both aliphatic and aromatic carbon atoms. These samples with low uranium content give measurable Rock-Eval hydrocarbon and organic-CO 2 yields, and C-13 NMR values of > 30% aliphatic carbon. In contrast, uranium-rich samples have few hydrocarbon pyrolysis products, increased Rock-Eval organic-CO 2 contents and > 70% aromatic carbon contents from C-13 NMR. The increase in aromaticity and decrease in hydrocarbon pyrolysis yield are related to the amount of uranium and the age of the uranium minerals, which correspond to the degree of radiation damage. The three analytical techniques give complementary results. Increase in Rock-Eval organic-CO 2 yield correlates with uranium content for samples from the Grants uranium region. Calculations show that the amount of organic-CO 2 corresponds to the quantity of uranium chemically reduced by the organic matter for the Grants uranium region samples.

Applied Geochemistry↗

USGS2007

In situ quantitative analysis of individual H2O-CO2 fluid inclusions by laser Raman spectroscopy

Raman spectral parameters for the Raman ??1 (1285??cm- 1) and 2??2 (1388??cm- 1) bands for CO2 and for the O-H stretching vibration band of H2O (3600??cm- 1) were determined in H2O-CO2 fluid inclusions. Synthetic fluid inclusions containing 2.5 to 50??mol% CO2 were analyzed at temperatures equal to or greater than the homogenization temperature. The results were used to develop an empirical relationship between composition and Raman spectral parameters. The linear peak intensity ratio (IR = ICO2/(ICO2 + IH2O)) is related to the CO2 concentration in the inclusion according to the relation:Mole % C O2 = e- 3.959 IR2 + 8.0734 IRwhere ICO2 is the intensity of the 1388 cm- 1 peak and IH2O is the intensity of the 3600 cm- 1 peak. The relationship between linear peak intensity and composition was established at 350????C for compositions ranging from 2.5 to 50??mol% CO2. The CO2-H2O linear peak intensity ratio (IR) varies with temperature and the relationship between composition and IR is strictly valid only if the inclusions are analyzed at 350????C. The peak area ratio is defined as AR = ACO2/(ACO2 + AH2O), where ACO2 is the integrated area under the 1388??cm- 1 peak and AH2O is the integrated area under the 3600??cm- 1 peak. The relationship between peak area ratio (AR) and the CO2 concentration in the inclusions is given as:Mole % C O2 = 312.5 AR. The equation relating peak area ratio and composition is valid up to 25??mol% CO2 and from 300 to 450????C. The relationship between linear peak intensity ratio and composition should be used for inclusions containing ??? 50??mol% CO2 and which can be analyzed at 350????C. The relationship between composition and peak area ratios should be used when analyzing inclusions at temperatures less than or greater than 350????C (300-450) but can only be used for compositions ??? 25??mol% CO2. Note that this latter relationship has a somewhat larger standard deviation compared to the intensity ratio relationship. Calibration relationships employing peak areas for both members of the Fermi diad (??1 at 1285??cm- 1 and 2??2 at 1388??cm- 1) were slightly poorer than those using only the 2??2 (1388??cm- 1) member owing to interference from quartz peak at approximately 1160??cm- 1. The technique has been applied to natural low-salinity H2O-CO2 inclusions from the Butte, Montana, porphyry copper-molybdenum deposit. Carbon dioxide concentrations obtained range from below detection to 4.2??mol% CO2, and are in good agreement with concentrations determined previously based on microthermometric and petrographic observations. ?? 2007 Elsevier B.V. All rights reserved.

Chemical Geology↗

USGS1995

Ground-water quality in agricultural areas, Anoka Sand Plain Aquifer, east-central Minnesota, 1984-90

Ground-water quality in the Anoka Sand Plain aquifer was studied as part of the multiscale Management Systems Evaluation Area (MSEA) study by collecting water samples from shallow wells during August through November 1990. The sampling was conducted to: (1) aid in selection of the MSEA research area; (2) facilitate comparison of results at the MSEA research area to the regional scale; and (3) evaluate changes in ground-water quality in the Anoka Sand Plain aquifer since a previous study during 1984 through 1987. Samples were collected from 34 wells screened in the upper 6 meters of the surficial aquifer and located in cultivated agricultural areas. Water temperature, pH, specific conductance, and presence or absence of triazine herbicides were determined at all sites and samples from selected wells were analyzed for concentrations of dissolved oxygen, alkalinity, major cations and anions, nutrients, and selected herbicides and herbicide metabolites. The results of the study indicate that the water-quality of some shallow ground water in areas of predominantly agricultural land use has been affected by applications of nitrogen fertilizers and the herbicide atrazine. Concentrations of nitrite plus nitrate nitrogen (nitrate-N) in 19 samples ranged from less than the detection limit of 0.1 to 21 milligrams per liter (mg/L) with a median of 10 mg/L. Concentrations of nitrate-N were not significantly correlated with depth below the water table or dissolved oxygen but were significantly correlated with concentrations of chloride. Concentrations of nitrate-N during 1990 were generally similar to concentrations measured during 1984 through 1987. Changes in concentrations of nitrate-N during 1984 through 1990 were likely related to variations in recharge or other site-specific factors. Immunoassay analyses were used as screening tools to detect the presence of triazine herbicides. All samples in which triazine herbicides were detected by immunoassay, and selected samples in which triazine herbicides were not detected by immunoassay, were analyzed for selected herbicides and herbicide metabolites by gas chromatography/mass spectroscopy (GC/MS). There was an excellent correspondence between concentrations of triazine herbicides indicated by immunoassay and concentrations of atrazine measured by GC/MS, indicating that the immunoassay method was a valuable qualitative to semi-quantitative tool for evaluating the presence and approximate concentration of atrazine. The combined results of immunoassay and GC/MS analyses indicate that atrazine was detected in 11 of the 34 wells with a median concentration less than the immunoassay detection limit of 0.1 micrograms per liter ( μ g/L). Atrazine was detected in 11 of the 17 samples analyzed by GC/MS at concentrations ranging from the detection limit of 0.05 to 0.81 μ g/L with a median of 0.09 μ g/L. Atrazine metabolite de-ethylatrazine (DEA) was the most frequently detected herbicide or herbicide metabolite and generally was present at the greatest concentrations. There were detections of DEA in 13 of the 17 samples analyzed at concentrations ranging from the detection limit of 0.05 to 1.12 μ g/L with a median of 0.15 μ g/L. Concentrations of DEA were significantly correlated with concentrations of calcium, magnesium, and specific conductance. The atrazine metabolite de-isopropylatrazine and the herbicide metolachlor both were detected in 1 of the 17 wells. The frequency of detection and the concentrations of atrazine in shallow ground water during 1990 were very similar to results of sampling conducted in 1984. Concentrations of atrazine and DEA generally were greater near the water table and decreased or were not detected in deeper wells. All of the samples in which atrazine and DEA were detected also had increased (greater than 3 mg/L) nitrate-N concentrations. However, not all samples with increased concentrations of nitrate-N had detections of atrazine or DEA. This likely indicates either that there were sources of nitrate-N other than cultivated fields on which both atrazine and nitrogen were applied or that nitrate-N reached ground water more readily than atrazine or DEA.

Minnesota↗

USGS2017

Analysis of artificially matured shales with confocal laser scanning raman microscopy: Applications to organic matter characterization

Raman spectroscopy has been suggested as a method for characterizing the thermal maturity of rocks. The literature contains many empirical correlations between thermal maturity proxies, such as vitrinite reflectance (V Ro ) and pyrolysis-T max , with spectral metrics such as Raman peak-widths, peak-center positions, peak-areas and all manner of differences and ratios of these parameters. However, while these correlations may be convincing for small data sets from limited sample series, broader application of these metrics to disparate and heterogeneous samples proves difficult and there remains no consensus. In this extended abstract, Raman spectroscopy is introduced and the history of Raman analysis of carbonaceous material is briefly outlined, highlighting some of the latent difficulties and potential sources of bias. We suggest the organization of a community working group to establish terminology, guidelines, procedures and standards necessary for the successful development of this technique to characterize organic matter in an accessible, unbiased, and reproducible manner. For the present multi-phase study, immature shale samples from the Bakken and Duvernay formations were subjected to hydrous pyrolysis for 72 hours at temperatures from 280°C to 360°C. Rock residues were mounted and polished for analysis via confocal laser-scanning Raman microscopy and reflectance. The maturation series from the Bakken was randomized for the Phase-I single-blind study to be presented at this conference. For the Phase-II study, solid bitumen reflectance (B Ro ) values for the Duvernay series will be known. Multiple hyperspectral maps were collected from each Bakken sample, with each map consisting of a single diffraction-limited spot-size spectrum per 1 µm 2 in rectangular areas several hundred micrometers on a side. Initial attempts at using basic spectral metrics on small numbers of hand-selected spectra to sort the blind series produced inconclusive results: any number of possible correlations could be found. In an improved approach, the statistics of the full spectral datasets were leveraged to: 1) objectively identify organic carbon types (OCTs) in a given map based on Raman and fluorescence spectral characteristics, 2) identify those OCTs in other maps from the same sample and determine if the heterogeneity of the sample has been adequately characterized, and 3) identify the same OCTs in maps from other samples in the maturation series. In ongoing work, our goals are to: 1) use these analyses of the blind series to develop a hypothesis for a correlation to maturation, 2) test the hypothesis by applying the same analyses to the known Duvernay series (in Phase-II), 3) if necessary refine the hypothesis based on observations from the Duvernay analysis, and 4) finally reveal the true order of the Bakken series to verify if the hypothesized correlation accurately predicts the maturity order of the samples. In this document, we share progress to date. The analysis of one area of interest is detailed showing the differentiation of two OCTs based on Raman and fluorescence spectral features, including the use of 2-factor histograms, Principle Components Analysis (PCA), and Nonlinear Iterative Peak Fitting (NIPF).

Conference Paper↗

USGS2021

Biodiversity effects on grape quality depend on variety and management intensity

Interactions between plants can be beneficial, detrimental or neutral. In agricultural systems, competition between crop and spontaneous vegetation is a major concern. We evaluated the relative support for three non-exclusive ecological hypotheses about interactions between crop and spontaneous plants based on competition, complementarity or facilitation. The study was conducted in Swiss vineyards with different vegetation management intensities. In all, 33 vineyards planted with two different grape varieties were studied over 3 years to determine whether low-intensity vegetation management might provide benefits for grape quality parameters. Management intensity varied with the degree of control of spontaneous inter-row vegetation. Features of spontaneous vegetation measured included total cover, total species richness and abundance of nitrogen-fixing plants. Grape quality parameters of known importance to wine making (yeast assimilable nitrogen, sugars, tartaric acid and malic acid) were determined by Fourier-transform infrared spectroscopy (FTIR). Using structural equation modelling, we evaluated hypotheses about the multivariate responses of grape quality parameters as well as the direct and indirect (plant-mediated) effects of management. Observed effects of management differed between grape varieties. Management intensity and abundance of N-fixing plants significantly influenced grape quality parameters while total richness of spontaneous plants did not have detectable effects. Abundance of N-fixing plants was enhanced by low-intensity management resulting in increased N content in the red grape variety Pinot noir , potentially enhancing grape quality, while measured soil N content did not explain the increase. Synthesis and applications . Our study shows that crop quality can be enhanced by spontaneous plants, in this case by the abundance of a key functional group (N-fixers), most likely through plant–plant or plant–microbe facilitation. However, beneficial interactions may have a high specificity in terms of facilitation partners and may have contrasting effects at low taxonomic resolutions such as crop varieties. Generally, increasing plant biodiversity in agricultural systems may increase competition with crops. Thus, the identification of suitable interaction partners and a careful balance between crop variety and spontaneous plant species may be necessary to utilize beneficial interactions and to reduce the trade-off between agricultural production and biodiversity to achieve a sustainable ecological benefit in agricultural systems.

Canton of Valais↗

USGS2025

Properties of solid bitumen formed during hydrous, anhydrous, and brine pyrolysis of oil shale: Implications for solid bitumen reflectance in source-rock reservoirs

Solid bitumen reflectance (BR o in %) is widely used as a thermal maturity proxy in source-rock reservoirs, yet solid bitumen texture and physical attributes may be affected by varying environmental constraints during its formation, e.g., water saturation, mineral catalysis, or salinity. Herein we investigated the development of solid bitumen properties during artificial maturation using three diverse (lacustrine to marine) oil shale samples containing abundant amorphous H-rich sedimentary organic matter (bituminite). The oil shales were treated via pyrolysis (320 °C, 72 h) using hydrous, anhydrous, and brine conditions, causing the development of a newly formed solid bitumen in the experiment residues from the thermal conversion of bituminite. The properties of the newly formed solid bitumen then were evaluated via geochemical screening tests, optical and electron microscopy, and infrared spectroscopy. Experimental residues also were treated via solvent extraction, allowing characterization of the effects of extraction on solid bitumen. Results showed that bituminite with higher resin and asphaltene components evolved to a solid bitumen with higher reflectance (as a percentage of the original value) when exposed to the same heat treatment, relative to bituminite with higher saturate and aromatic components. Aromatization of solid bitumen also was generally more pronounced in the presence of deionized water relative to anhydrous conditions, supporting prior observations. These results suggest the compositions of primary sedimentary organic matter, and the local concentration of water, affect the development of solid bitumen during thermal advance, potentially explaining the origin of multiple solid bitumen populations with varying reflectance in source-rock reservoir samples or in a single microscope field. Experiments using brine were inconclusive regarding enhanced/decreased aromatization, which could be attributed to the salinities of the brines used in the tests. Extraction of residues caused a consistent increase in BR o values, suggesting that migrating or expelled oils could cause an increase in BR o via natural solvation and absent an increase in temperature. This work provides insights into the development and evolution of BR o in source-rock reservoirs as a function of the composition of the original bituminite and changing environmental conditions, with potentially broad application for petroleum prospecting and resource estimation.

Colorado↗